Method of dyeing cellulose fibers



United States Patent 3,411,860 METHOD OF DYEING CELLULOSE FIBERS Willy Braun, Heidelberg, and Julius Eisele, Guenter Krehbiel, Guenter Lange, Roland Mueller, Wilhelm Ruemens, Josef Stadler, and Hermann Weissauer, Ludwigshafen (Rhine), Germany, assignors to Badische Anilin- & Soda-Fabrik Aktiengesellschaft, Ludwigshafen (Rhine), Germany No Drawing. Filed Oct. 28, 1958, Ser. No. 770,018 Claims priority, application Germany, Oct. 29, 1957, B 46,595 1 Claim. (Cl. 318) This invention relates to a method of dyeing cellulose fibers in the presence of compounds which are capable of forming aminoplasts.

The most important aspect of the invention consists in the fact that the dyeing is carried out in a dyebath containing a dyestulf which includes in the molecule of at least one methylol group or one reactive hydrogen atom which takes up formaldehyde as a methylol group, and that the dyebath contains in addition at least one aminoplast-forming compound including one or more methylol groups. Instead of the aminoplast-forming compound including at least one methylol group, there may also be added to the dyebath the initial product of this compound, which does not as yet contain any methylol group but which forms this with formaldehyde, together with formaldehyde or a compound splitting off formaldehyde. The methylol group or the reactive hydrogen atom in the dyestuff, together with the aminoplast-forming compound or its initial product, are of special importance in the process according to the invention because it is thanks to this dyestuff that the process now produces eifects which are particularly pleasing and surprising for both the dyer and the user. That is to say, the dyestuffs are not merely embedded in the aminoplast and fixed on to the threads by means of this, but are also attached to the aminoplast and the threads in a very close bond. The dyeings are therefore especially fast to washing and rubbing. In addition, cottons, .for example, may now be dyed with dyestuffs which are not in themselves cotton dyestuffs.

One object of this invention is to obtain fast dyeings on fibers. A further object is to combine dyestufis with fibers by means of aminoplast-forming compounds. A further object is to produce dyeings of good fastness properties on cellulose fibers particularly when the dyestuff and the fiber have a low afiinity for each other. A further object is to combine the step of dyeing with the step of finishing with aminoplast finishes. A further object is to apply on fibers simultaneously with dyestuffs and aminoplast-forming compounds, additional textile finishing compounds, such as hydrophobing agents, softening agents, stiffening and/ or sizing agents.

These and further objects of the invention are achieved by applying on fibers a liquid which contains water, hydrogen ion donating agents, organic textile dyestuffs which contain in the molecule at least one hydrogen atom which has been substituted by a methylol group, and hardenable aminoplast-forming compounds which contain in the molecule at least one methylol group attached to a nitrogen atom, and then subjecting the fibers to a heat treatment at elevated temperatures. It is also possible to wet the fiber with the liquid which contains the dyestutf and the aminoplast-forming compound but does not contain the hydrogen ion donating agent and then to bring together the fibers wetted in such a way with the hydrogen ion donating agent. Alternatively the method of this invention can be carried out by applying those dyestuffs which contain in the molecule hydrogen atoms which can be substituted by methylol groups by reacting with formaldehyde or formaldehyde yielding compounds and/or 3,411,860 Patented Nov. 19, 1968 the precursors of the aminoplast-forming compounds which are capable of adding methylol groups, together with formaldehyde or a formaldehyde yielding compound.

The term hardenable means that the aminoplast-forming compounds form high molecular weight condensation products under the influence of hydrogen ion donating agents and elevated temperatures. Hardenable aminoplastforming compounds are known as finishing agents for textiles, for example as creaseproofing agents for cotton.

Suitable hardenable aminoplast-forming compounds are methylol derivatives of low molecular weight nitrogenous compounds, and indeed those which contain at least once in the molecule a group of the formula:

in which X is O, S, N, or NH, and R is hydrogen or an alkyl, cycloalkyl or aryl radical of which the carbon chain or ring may if desired be interrupted by one or more hetero atoms. When in the above mentioned group X is N, it can be a member of the triazine ring when taken together with its carbon atom. In the triazine ring, not only one carbon atom but also a second and the third carbon atom can be substituted by an amino group. R in the above mentioned group can also be and therefore when taken together with the nitrogen atom and with the carbon atom can be a l-keto-trimethylenetriamine ring. Furthermore, R can be a methylene chain and therefore when taken together with the nitrogen atom and with the carbon atom can be a member of a lactam ring, preferably with 3, 4, 5, or 6 methylene groups. Furthermore, R can be an ethylene group which is linked with the nitrogen atom of another methylol amino group which is attached to the free valency of the carbon atom in the above mentioned formula. In this case ethylene urea and its derivatives are present. As examples of hardenable aminoplast-forming methylol compounds which can be used in accordance with the present invention, the following can be mentioned: dimethylolurea; dimethyldimethylolurea; dimethyloldicyandiamide; methylolthiourea; dimethylolguanidine; trimethylolmelamine; diphenyldimethylolurea; the methylol derivatives of monoand diureines, carboxylic acid amides and diamides, preferably of aliphatic carboxylic acids and dicarboxylic acids with from 2'to 8 carbon atoms; urethanes and polyurethanes, preferably of alcohols and glycols with from 2 to 6 carbon atoms, for example butane-diol diurethane. The methylol derivatives of l-keto-trimethylene-triamine compounds, also referred to as triazones, furthermore lactams, polyamides and ethylene ureas are also suitable. Instead of melamine which is an aminotriazine with 3 amino groups there are also suitable amino triazines with 1 or 2 amino groups.

By precursors of aminoplast-forming substances, there are to be understood compounds which contain in the molecule at least once the group of the formula:

in which X and R have the above-specified significance.

The hardenable aminoplast-forming substances, i.e. methylol compounds, are formed from these substances in the presence of formaldehyde or compounds which split off formaldehyde. The combination of such precursors and formaldehyde or compounds splitting off formaldehyde will hereinafter be designated by the expression aminoplast-forming substances.

The hardenable aminoplast-forming substances may also be combined with the precursors and/ or aldehydes or compounds splitting off formaldehyde in the process of this invention. Mixtures of several hardenable aminoplast-forming compounds or mixtures. of several precursors of the aminoplast-forming compounds may also be used.

As compounds splitting off or yielding formaldehyde there may be used paraformaldehyde or hexamethylene tetramine. In admixture with formaldehyde or the formaldehyde yielding compounds there may be present other aldehydes, such as acetaldehyde or glyoxal.

The organic textile dyestuffs containing methylol groups which can be used for dyeing according to this invention may be obtained for example by treating organic textile dyestuffs or dyestuff intermediates which contain reactive, i.e. loosely combined hydrogen atoms with formaldehyde or compounds supplying formaldehyde in a Weakly acid to alkaline medium, especially a pH-value of 6 to 11. These dyestuffs are named in the following description methylol dyestuffs. The phrase organic textile dyestuffs includes organic dyes, e.g. azo or anthraquinone dyes, which can be used for dyeing textile materials Without any further measures, e. g. watersoluble dyes or dispersion dyes. Both inorganic and organic pigments are excluded.

As initial materials for the production of methylol dyestuffs there may be used organic textile dyestufis of a great variety of classes, as for example azo or anthraquinone dyestuffs which contain reactive hydrogen atoms. The latter are hydrogen atoms which can be replaced by organic substituents and may be present for example in activated methylene groups, in phenolic hydroxyl or sulfhydryl groups, and also in carboxylic acid amide, sulfonic acid amide, urea or thiourea groupings or in heterocyclic radicals, such as laetam, thiolactam or melaminelike radicals. It is of course necessary that these reactive hydrogen atoms should indeed be replaceable by organic substituents. By reason of the so-called steric hindrance, e.g. in the case of the hydrogen atoms in the phenolic hydroxyl groups of phenols and naphthols by an azo group in neighbouring position to the hydroxyl group, this need not always be the case. Those dyestuffs of the above-mentioned classes are especially suitable as initial dyestufis for the process according to this invention which already contain one or more solubilizing groups, as for example sulfonic acid or carboxylic acid radicals, which may be substituted, sulfonic acid amide or carboxylic acid amide groups, alkyl, aryl, aralkyl or cycloalkyl sulfone groups. They may also be substituted by substantially neutral atoms or groups, such as halogen atoms or nitro, hydroxy, alkyl, alkoxyl, hydroxyalkyl, amino or acylamino groups.

Precursor dyestuffs for the reaction with formaldehyde or agents yielding formaldehyde are for example azo, or anthraquinone dyestuffs which contain reactive hydrogen atoms. These dyestuffs are capable of forming methylol groups and may therefore be used directly in the process of this invention. An advantageous method of preparing methylol dyestuffs is described in the copending application Ser. No. 735,704, Braun et al., filed May 16, 1958 now abandoned.

These dyestuffs are also suitable for the dyeing process according to the present invention. It is pointed out that the methylol group in the dyestuffs or the ability of forming mehylol groups in the presence of formaldehyde or formaldehyde yielding compounds is the essential feature of dyestuffs with which the fibers are to be dyed. The formulae of the dyestuffs are of minor importance and the invention is not restricted to organic textile dyestuffs of a particular kind.

The dyestuffs may be Water-soluble, but they may also be difiicultly soluble or insoluble in Water. The dyestuffs which are insoluble in water are preferably used in finely divided form in this process. However, We prefer in the process of this invention to use those of the methylol dyestuffs which are water-soluble at least at the temperature of the dyeing bath.

Hydrogen ion donating agents are acids or potential acid donors which are capable of promoting the condensation reaction of the methylol groups and, if formaldehyde or formaldehyde yielding compounds are in the liquid for the treatment of the fibers, are capable of promoting the substitution of reactive hydrogen atoms by methylol groups. It is not necessary that the amount of these agents be sufficient to give an acid dyeing medium. Very small amounts of hydrogen ions are sufficient for inducing or initiating the condensation reaction by their catalytic action while heating.

The acids in the presence of which the goods to be dyed are treated may be inorganic or organic acids. Boric acid, phosphoric acid, formic acid, acetic acid, glycolic acid, tartaric acid, chloracetic acid, chloropropionic acid, citric acid, maleic acid and many others may be used. Acid-reacting compound which may be used instead of the acids or additionally thereto are for example salts which react acid in solution. Ammonium or amine salts of strong inorganic and organic acids, such as ammonium chloride and diethanolamine hydrochloride belong to this class. It is sufficient if the acid action of the hydrogen ion donating agents takes place'only at elevated temperature or when the methylol compounds arg present. From the great number of hydrogen ion donating agents which are capable of promoting the condensation reaction of hardenable aminoplast-forming compounds and which can be applied in the presence of textile fibers, those skilled in the art can easily select a suitable agent.

The dyestuffs and the aminoplast-forming substances are preferably applied to the textiles from an aqueous medium either by impregnation on the foulard or on the reel vat, on the jigger or on any other dyeing apparatus, for example on a cross spool dyeing apparatus. The temperature of the dye liquor may be 20 to C. Higher temperatures, for example up to C., such as prevail in closed systems under pressure, are also permissible. It is also possible however to apply the dyestuffs and the hardenable aminoplast-forming substances from solventcontaining emulsions or emulsified mixtures in which the dyestuff and the aminoplast-forming substance are present in the inner aqueous phase. The materials thus treated are then dried and subjected to a heat treatment at a temperature between 50 and 200 C., advantageously between 70 and C.

The process in accordance with the present invention is also advantageous for local dyeing such as is carried out in cloth printing with the addition of thickening agents such as British gum or tragacanth. We use the terms liquid, dyeing liquid or impregnating liquor in accordance with this invention for all combinations of water with methylol dyestuffs or dyestuffs capable of taking up methylol groups, with the hardenable aminoplast-forming compounds or their precursors being capable of taking up methylol groups, optionally with hydrogen ion donating agents and/ or optionally with formaldehyde or formaldehyde yielding compounds and/ or optionally with further dyeing or textile auxiliaries. Dyeing baths and printing pastes are encompassed by the above mentioned terms. However, We prefer dyeing liquids which contain preponderant amounts of water besides the other finely dispersed ingredients and which are thinly liquid. It is pointed out in accordance with this feature of the invention that at least the dyestuif and the aminoplast-forming compound or the precursors should be present in the dyeing liquid when it is applied on the fibers. Formaldehyde or formaldehyde yielding compounds should also be present in the liquid when dyestuffs Without methylol groups and only precursors of aminoplast-forming compounds are applied.

The amounts of the dyestuff or the methylol dyestuff and the amounts of the aminoplast-forming compound or its precursor which have to be present in the dyeing liquid may be varied within wide limits. The amount of the dyestuff depends, for example, on the depth of the shades wanted. In general, 2 to 40 grams, preferably 5 to 30 grams, of the dyestuif or the dyestutf mixture per liter of water or water-containing liquid are suitable. The amount of the aminoplast-forming compound or of mixtures of several aminoplast-forming compounds, and/or their precursors, or of mixtures of precursors with formaldehyde or formaldehyde-yielding compounds may also be varied within wide limits, for example, between 20 and 150 grams per liter of watet or water-containing liquid. The higher the amount of aminoplast-forming compound or its precursor employed in the dyebath, the higher will be the finishing effect obtained together with the dye applied to the fiber. The ratio between the dyebath liquid and hydrogen donating agent may be, for example, 1 liter to about 2 to 20 grams or more.

With the dyeing process according to this invention there may be combined a creaseproof, embossing, chintz and shrink-proof finishing. For this purpose fundamentally the same measures are carried out as are necessary for the above-described dyeing process. The additional effects are caused by the nature and amount of the aminoplastforming substances and the further mechanical improving process after drying.

Beside the dyestuffs and the aminoplast-forming substances, there may also be contained in the impregnating liquor, in so far as this is desirable or necessary, the otherwise usual hydrophobing, softening, leveling, wetting and dressing agents and also solutions or dispersions of plastics, epoxy resins or polyglycolacetals.

Hydrophobing agents are, for example, the known parafiin wax emulsion containing aluminum or zirconium. Suitable softening agents are, for example, hydroxyethylation products of high molecular weight fatty acids, fatty alcohols or fatty acid amides, high molecular weight polyglycol ethers, esters of high molecular weight fatty acids, fatty alcohol sulfonates, stearylethylene-imine-urea and stearoylamidomethyl pyridinium chloride. As leveling agents there may be used, for example, water'soluble salts of acid esters of polybasic acids which have been reacted with ethylene oxide or propylene oxide. Wetting agents are, for example, salts of alkylnaphthalene sulfonic acids and the alkali salts of sulfonated succinic acid dioctyl ester.

As dressing agents there may be mentioned cellulose ethers or esters and alginates. Suitable plastic solutions or dispersions are, for example, those on the basis of polyamides, polyvinyl ethers, polyvinyl alcohols, polyacrylic acid or their esters and amides as Well as the corresponding polymethacrylic compounds, polyvinyl propiopolymers, for example, of vinyl chloride and acrylic acid esters, butadiene and styrene or acrylonitrile, or of as-dichlorethylene, beta-chloralkylaryl acid esters, vinyl-betachlorethyl ether with acrylarnide or the amides of crotonic acid and maleic acid may also be used, and furthermore isoand di-iso-cyanates, polyethylene imines and also polyamines, silicic acid esters and silicones.

The term cellulose fibers includes flocks, staple fibers, threads, filaments, knitted fabrics, woven fabrics and felts. The fibers treated in accordance with this invention can be natural and regenerated natural materials, suchas cotton, linen or regenerated cellulose.

By the process according to this invention it is possible to dye, dress and finish the fibers in one working operation. The fibers may be dyed and simultaneously finished in a few minutes. The working period otherwise necessary for this purpose can be reduced from hours to a few minutes. Moreover the dyeings exhibit excellent wet fastness properties.

The following examples will further illustrate this invention but the invention is not restricted to these examples. The parts are parts by weight.

EXAMPLE 1 A bleached cotton fabric is impregnated on the foulacd at to C. with a liquor which contains per liter 20' grams of the dyestuif prepared according to the second paragraph of this example, grams of dimethyldimethylolurea and 4 grams of monoammonium phosphate, squeezed, then dried for example on a pin stenter at about C. and then heated for 4 minutes at C. The dyeing obtained is characterized by good fastness properties.

A diazonium solution prepared in known manner for 10.9 parts of 1-amino-3-hydroxybenzene is stirred into a solution of 23.9 parts of Z-amino-S-hydroxynaphthalene- 7-sulfonic acid, 4 parts of sodium hydroxide and 21.2 parts of anhydrous sodium carbonate in 350 parts of water. When the coupling has ended, the dyestutf formed is precipitated by the addition of sodium chloride and filtered off by suction. It is then stirred into 200 parts of a 15% aqueous formaldehyde solution with the addition of 4 parts of sodium hydroxide for 24 hours at 15 to 20 C., then precipitated with sodium chloride, filtered off by suction and dried at normal temperature in vacuo. It dyes cellulose fibers red-brown shades of very good fastness to wet treatment.

Instead of the dyestuff prepared according to the above direction, there may also be used the dyestuffs given in nate, polyacrylic acid esters or polyvinyl pyrrolidone. Co- 50 the following table.

Dyestutf Color H2NSO +N=N(|3Hfi H NH: Yellow o=o N o oas- -N=N- Red.

l ()H fi-NHz OCH3 (RH Red.

Dyestufi Color O H I l l S OzNHz S1036 Blue: I IHNH-CN1Ia EXAMPLE 2 70 second paragraph of this example, 80 grams of methylolmelamine methyl ether, 1.5 grams of the ammonium salt A cotton fabric which has been bleached, treated with of polyacrylic acid, 5 grams of polyglycol ether, 1 gram of caustic soda solution and acidified with acetic acid is imthe sodium salt of isopropylnaphthalene sulfonic acid and .pregnated on a foulard with a liquor which contains per 8 grams of a mixture of diethanolamine and triethanolaliter 18 grams of the dyestutf prepared according to the 75 mine hydrochlorides, squeezed, then dried at about 120 C. on a flat frame and subsequently heated for to minutes at 145 C. The dyeing obtained is characterized by good fastness properties. The fabric is moreover crease-resistant. For improving the handle, it may be subsequentiy washed with soap and soda, for example on a igger.

A diazonium solution prepared in known manner from 17.2 parts of N-(4-amino)-phenylurea is allowed to flow into a solution of 17.6 parts of the sodium salt of l-hydroxy-Z.4-dimethylolbenzene and 21.2 parts of anhydrous sodium carbonate in 200' parts of water. When the coupling is ended, the dyestuff is precipitated by the addition of solid sodium chloride, filtered off by suction and dried in vacuo at normal temperature. On cellulose fibers the dyestuffgives brownish-yellow dyeings of very good fastness to wet treatment.

EXAMPLE 3 A staple fiber fabric is padded on a foulard with a liquor which contains per liter grams of the dyestuff prepared according to the second paragraph of this example, 60 grams of dimethylolbutane-diol-diurethane, 40 grams of dimethylolurea, 1 gram of polyacrylamide, grams of a aqueous paste of the condensation product of 1 mol of stearic acid and 1 mol of dihydroxyethyldiethylene triamine and 5 grams of ammonium nitrate. The fabric is dried up to a residual moisture content of about 10%, corrugated on a Schreiner calender under pressure at 170 C. and then heated for 5 to 10 minutes at 150 C. For modifying the handle, the fabric may be thereafter washed on an open-width washing machine with soap and soda. The dyeing thus obtained exhibits good fastness properties. The embossed effect is washproof.

20 parts of 30% aqueous formaldehyde solution are added to a solution of 4 parts of sodium chloride and 9.4 parts of phenol in 10 parts of water and the reaction mixture allowed to stand for 24'hours. The clear yellow liquid formed has added to it a solution of 15.9 parts of anhydrous sodium carbonate in 100 parts of water and then a diazo solution prepared in known manner from 24.2 parts of 1-amino-3.4-dichlorbenzene-5-sulfonic acid. After the coupling has ended, the dyestutf formed is salted out by the addition of sodium chloride, filtered off and dried in vacuo at normal temperature. It dyes wool, spun rayon staple fiber and cotton brilliant reddish-yellow shades of very good fastness to wet treatment.

EXAMPLE 4 A bleached and mercerized linen fabric is padded on a foulard with a liquor which contains per liter 20 grams of 1 amino-4-(4-ureidophenyl)-aminoanthraquinone-2- sulfonic acid obtained by reacting equimolecular amounts of 1-amino-4-bromanthraquinone-Z-sulfonic acid with 4- aminophenyl urea in an aqueous medium in the presence of sodium bicarbonate, 100 grams of dimethylol urea, 2 grams of ammonium polyacrylate, 20 grams of crystal oil, 20 grams of dodecyl silicate, 2 grams of the reaction product of 1 mol of octadecyl alcohol with 6 mols of ethylene oxide and 6 grams of tartaric acid, dried to a residual moisture content of about 6%, calendered under pressure at elevated temperature and then heated for 3 to 4 minutes at 150 C. Then the fabric may be subjected to a treatment with soap and soda. The fabric is dyed fast and exhibits a smooth soft handle. The resistance to creasing is very good.

EXAMPLE 5 A cotton fabric is impregnated on a jigger with a liquor which contains per liter 10 grams of the red dyestuff prepared according to the second paragraph of this example, 80 grams of a methylol compound of urea and melamine (ratio of urea to melamine 3:7), 8 grams of an about aqueous dispersion of a copolymer of parts by weight of as-dichloroethylene, 45 parts by weight of butyl acrylate and 5 parts by weight of polyacrylamide, 5 grams of a polyglycol ether from 1 mol of sperm oil alcohol and 18 mols of ethylene oxide and 5 grams of monoammoniurn phosphate, squeezed, dried to a residual moisture content of about 10%, embossed on an embossing calender at 180 to 200 C. under pressure and subsequently heated for 10 minutes at 135 C. It may then be washed with soap and soda or a fatty alcohol sulfonate in an openwidth washing machine. The embossed effect is waterproof and the dyeing exhibits very good fastness properties.

17.3 parts of 1-aminobenzene-4-sulfonic acid are diazotized in the known manner and the aqueous solution of the diazonium salt is stirred into a solution of 28.2 parts of 2-ureido-5-hydroxynaphthalene-7-sulfonic acid, 4 parts of sodium hydroxide and 21.2 parts of anhydrous sodium carbonate in 350 parts of water. When the coupling has ended, the dyestuff is separated by the addition of sodium chloride. It is filtered off by suction, added to a mixture of 200 parts of 15% aqueous formaldehyde solution and 4 parts of sodium hydroxide solution and stirred therein for about 24 hours at 15 to 20 C. The dyestuff is then precipitated by the addition of sodium chloride, filtered off by suction and dried in vacuo at normal temperature. Its red-violet dyeings on cellulose fibers have very good fastness to wet treatment.

EXAMPLE 6 A bleached stap'e fiber fabric is impregnated on a foulard with a liquor which contains per liter 20 grams of the dyestuff prepared according to the second paragraph of this example, 40 grams of dimethyldimethylolurea, grams of dimethylol-butane-diol-diurethane, 10 grams of methylolcaprylic lactam, 0.5 gram of polymethachylamide, 8 grams of stearylethylene-imine urea, 10 grams of poly-glycol ether and 5 grams of ammonium nitrate, squeezed, dried, and subsequently heated for 10 minutes at 150 C. The fabric thus treated is crease-resistant and shows a yellow-brown dyeing with very good fastness to wet treatment.

40 parts of a 30% aqueous formaldehyde solution are added to a solution of 4 parts of sodium hydroxide and 15.2 parts of N-(3-hydroxy)-phenylurea in 80 parts of water and the reaction mixture is allowed to stand for 20 hours at room temperature. To the resultant clear yellow liquid there is added a solution of 15.9 parts of anhydrous sodium carbonate in parts of water and then a diazo solution prepared in the usual way from 17 .2 parts of 1-aminobenzene-4-sulfonic acid amide. After the coupling has ended, the dyestuff formed is salted out by the addition of sodium chloride, filtered and dried at normal temperature in vacuo.

EXAMPLE 7 A mixed fabric of staple fiber and cotton which has been bleached and leached is padded on a foulard with a liquor which contains per liter 30 grams of the dyestuff according to Example 1, 3 grams of polyethylene imine, 10 grams of a 40% aqueous dispersion of a copolymer of 52 parts of acrylic acid beta-chlorethyl ester, 38 parts of ethyl acrylate and 4 parts of acrylamide, 5 grams of the bisulfite compound of hexamethylene diisocyanate, 20 grams of hexamethylene tetramine, 90 grams of trimethylolmelamine and 10 grams of diethanolamine hydrochloride, squeezed, dried, and heated for 10 minutes at C. If desired the fabric may be washed with soap and soda on an open-width washing machine to improve the handle. The dyeing thus obtained has very good fastness properties.

EXAMPLE 8 A bleached and leached cotton fabric is impregnated on a foulard with a liquor which contains per liter 20 grams of the dyestuff prepared according to the second paragraph of this example, and also 80 gram of dimethylol-glyoxal-monoureine and 5 grams of monoammonium phosphate. The fabric is squeezed, then dried at about 70 C. for example on a pin stenter and afterheated for minutes at about 150 C. The fastness prop erties of the fabric thus dyed are very good. Moreover it is crease-resistant. A fabric of cyanoethylated cotton can be treated in the same way.

25 parts of l-amino-4-(4'-ureidophenyl)-aminoanthraquinone-Z-sulfonic acid is made into a paste with 100 parts of water. After adding 50 parts of a 30% aqueous formaldehyde solution and 5.3 parts of anhydrous sodium carbonate, the reaction mixture is stirred for 24 hours at normal temperature, the dyestuff thereby gradually passing into solution. The dyestuif formed which contains methylene groups is Worked up as described above. It dyes wool and cotton brilliant blue shades of good fastness to wet treatment.

EXAMPLE 9 A mixed fabric of 50% of cotton and 50% of staple fiber is leached and bleached, and treated in a liquor which contains per liter 30 grams of the dyestuff prepared according to Example 5, 60 grams of urea, 200 grams of a 30% formaldehyde solution, or the corresponding amount of paraformaldehyde, 50 grams of a 40% paraffin wax emulsion containing aluminum and 2 grams of ammonium chloride, impregnated on a foulard, then dried at 90 C. on a pin stenter and heated for 4 minutes at 160 C.

EXAMPLE A bleached staple fiber fabric is impregnated with a liquor which contains per liter 5 grams of the dyestutf prepared according to Example 3, grams of dimethyldimethylolurea, 3 grams of methylol-caprylic lactam, 5 grams of stearoyl-aminomethylpyridinium chloride and 3 grams of ammonium oxalate, then dried on a pin stenter at 120 C. and subsequently heated for 10 minutes at 150 C.

EXAMPLE 11 A cotton fabric which has been bleached and printed is impregnated with a liquor which contains per liter 5 grams of the dyestuff prepared according to the second paragraph of Example 1, 70 grams of dimethylol ethylene urea and 12 grams of magnesium chloride, then squeezed,

dried, and heated for 5 minutes at 155 C. A dyeing having very good fastness properties is obtained.

EXAMPLE 12 A cotton fabric is impregnated with a liquor which contains per liter 10 grams of the dyestuff prepared according to the second paragraph of Example 3, 80 grams of dimethylol triazone (l-keto-trimethylene triamine) and 10 grams of zinc chloride, then squeezed, dried, and after-heated for 5 minutes at 155 C. A dyeing having very good fastness properties is obtained.

EXAMPLE 13 A fabric of regenerated cellulose whichhas been bleached and acidified with acetic acid is impregnated with a liquor which contains per liter 20 grams of the dyestuff prepared according to the second paragraph of Example 1, 50 grams of dimethylol ethylene urea, grams of an epoxy resin and 6 grams of zinc tetrafiuoborate, then squeezed, dried, and heated for 6 minutes at 155 C. A dyeing having very good fastness properties is obtained.

EXAMPLE 1 4 A bleached cotton fabric is impregnated with a liquor which contains per liter 18 grams of the dyestufi prepared according to the second paragraph of Example 5, 80

grams of dimethylol adipic acid diamine, 3 grams of a copolymer of acrylic acid and methacrylic acid (ratio by weight 1:1), 5 grams of polyglycol ether, 10 grams of methyl silicone and 10 grams of zinc chloride, then squeezed, dried and heated for 5' minutes at 155 C. A dyeing having very good fastness to wet treatment is obtained.

EXAMPLE 15 A mixed fabric of cotton and linen which has been bleached and printed is impregnated with a dye bath which contains per liter 8 grams of the dyestutf prepared according to the second paragraph of Example 5, 60 grams of a low molecular weight condensation product from urea, dicyandiamide and formaldehyde (molar ratio 1:l:1.8) ,which contains a methylol group, 4 grams of diammonium phosphate, 10 grams of a polyglycol ether, and 3 grams of stearyl ethylene imine urea.

The fabric thus treated is squeezed, dried to a residual moisture content of about 14%, treated twice on a chintz calender with 50% over-feed and then heated for 4 minutes at C. The dyeing obtained exhibits good fastness properties and the chintz finish of the fabric is washproof. Furthermore, the fabric is shrink-resistant.

EXAMPLE 16 A mixed fabric of cotton and regenerated cellulose which has been bleached and printed is impregnated with a dye bath containing per liter 12 grams of the dyestuif prepared according to the second paragraph of Example 3, 80 grams of a low molecular weight condensation product from urea, thiourea and formaldehyde (molar ratio 3:1:2), which contains a methylol group, 5 grams of stearyl amide methyl pyridinium chloride, 3 grams of polyvinyl alcohol and 3 grams of ammonium nitrate. The fabric thus treated is squeezed, dried and heated for four minutes at C. The dyeing thus obtained exhibits good fastness properties. Furthermore, the fabric is creaseand shrink-resistant.

The same result is obtained by using a low molecular weight condensation product from urea, guanidine and formaldehyde (molar ratio 4:1 :22) instead of the abovementioned condensation product from urea, thiourea and formaldehyde.

We claim:

1. In the process for simultaneously coloring and finishing a textile fabric formed at least in part of cellulose fibers by immersing said fabric in an aqueous solution containing a resin-forming composition, an acid catalyst and a water-soluble reactive dyestufi having a group which is reactive under acid conditions with said resin-forming composition to bond said dyestuff to said resin, drying the so-treated textile fabric and thereafter baking the textile fabric to effect the formation of said resin and said bond between said dyestulf and said resin, the improvement which consists in adding to said solutiorcil an alkali metal salt of an alkylnaphthalene sulfonic ac1 References Cited UNITED STATES PATENTS 2,093,651 9/1937 Widmer et al 8-54.2 2,416,884 3/1947 Schreiber et al. 8-1 l6.3 2,773,071 12/1956 Pizzarello et al. 260-380 2,880,052 3/1959 Conciatori et al 8116.3

NORMAN G. TORCHIN, Primary Examiner. T. J. HERBERT, Assistant Examiner. 

1. IN THE PROCESS FOR SIMULTANEOUSLY COLORING AND FINISHING A TEXTILE FABRIC FORMED AT LEAST IN PART OF CELLULOSE FIBERS BY IMMERSING SAID FABRIC IN AN AQUEOUS SOLUTION CONTAINING A RESIN-FORMING COMPOSITION, AN ACID CATALYST AND A WATER-SOLUBLE REACTIVE DYESTUFF HAVING A GROUP WHICH IS REACTIVE UNDER ACID CONDITIONS WITH SAID RESIN-FORMING COMPOSITION TO BOND SAID DYESTUFF TO SAID RESIN, DRYING THE SO-TREATED TEXTILE FABRIC AND THEREAFTER BAKING THE TEXTILE FABRIC TO EFFECT THE FORMATION OF SAID RESIN AND SAID BOND BETWEEN SAID DYESTUFF AND SAID RESIN, THE IMPROVEMENT WHICH CONSISTS IN ADDING TO SAID SOLUTION AN ALKALI METAL SALT OF AN ALKYLNAPHTHALENE FULFONIC ACID. 